Probing keto-enol tautomerism using photoelectron spectroscopy
2015 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 17, no 30, 19991-19996 p.Article in journal (Refereed) Published
We theoretically investigate the mechanism of tautomerism in the gas-phase acetylacetone molecule. The minimum energy path between the enolone and diketo forms has been computed using the Nudged-Elastic Band (NEB) method within the density-functional theory (DFT) using the projector augmented-wave method and generalized gradient approximation in Perdew-Wang (PW91) parametrization. The lowest transition state as well as several intermediate geometries between the two stable tautomers have been identified. The outer-valence ionization spectra for all determined geometries have been computed using the third-order non-Dyson algebraic diagrammatic construction technique. Furthermore, the oxygen core-shell ionization spectra for these geometries have been obtained using DFT and the Becke three-parameter Lee-Yang-Parr (B3LYP) functional. It is shown that all spectra depend strongly on the geometries demonstrating the possibility of following the proton-transfer dynamics using photoelectron spectroscopy in pump-probe experiments.
Place, publisher, year, edition, pages
2015. Vol. 17, no 30, 19991-19996 p.
Condensed Matter Physics
IdentifiersURN: urn:nbn:se:uu:diva-260745DOI: 10.1039/c5cp02023aISI: 000358347500034PubMedID: 26172609OAI: oai:DiVA.org:uu-260745DiVA: diva2:848263